(2R,3R,4S)-1-(tert-Butyl-dimethyl-silanyloxy)-7-(4-methoxy-benzyloxy)-2,4-dimethyl-hept-5-yn-3-ol | 236390-86-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R,3R,4S)-1-(tert-Butyl-dimethyl-silanyloxy)-7-(4-methoxy-benzyloxy)-2,4-dimethyl-hept-5-yn-3-ol
• 英文别名: (2R,3R,4S)-1-[tert-butyl(dimethyl)silyl]oxy-7-[(4-methoxyphenyl)methoxy]-2,4-dimethylhept-5-yn-3-ol
• CAS: 236390-86-6
• 化学式: C₂₃H₃₈O₄Si
• 分子量: 406.638
• InChiKey: AORDLHWSUYSFPK-NNMXDRDESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.87
• 重原子数：
  28
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (2R,3R,4S)-1-(tert-Butyl-dimethyl-silanyloxy)-7-(4-methoxy-benzyloxy)-2,4-dimethyl-hept-5-yn-3-ol 在 Lindlar's catalyst 正丁基锂 、 氢气 、 一溴化碘 、 碳酸氢钠 、 potassium carbonate 、 N,N-二异丙基乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 生成 (2R,3S,5S,6R)-1,7-Bis-(tert-butyl-dimethyl-silanyloxy)-3,5-bis-methoxymethoxy-2,4,6-trimethyl-heptane
  参考文献：
  名称：

  Synthesis of a syn,syn,syn,syn-Stereopentad Precursor of the Marine Sponge Polyketide Callystatin A

  摘要：

  A C13-22 syn,syn,syn,syn-stereopentad precursor of the cytotoxic polyketide callystatin A has been prepared. The synthesis involved BF3-promoted addition of the (M)-allenylstannane 28 to the alpha-methyl-beta-OTBS aldehyde 8 to afford the syn,syn adduct homopropargylic alcohol 29. Protection as the cyclic anisylidene acetal 31 and reduction of the acetylenic triple bond with Red-Al gave the (E)-allylic alcohol 32. This was subjected to Sharpless asymmetric epoxidation and subsequent treatment with an ethylcopper reagent to yield diol 34; hydrogenolysis of the derived tosylate 37 with LiBEt3H afforded 38. Acetal hydrogenolysis with DIBAl-H and oxidation yielded aldehyde 40 which was subjected to Horner-Emmons homologation to afford ester 41. This ester was converted to ester 44, an intermediate in the Kobayashi synthesis, with which it was found to be identical.

  DOI：

  10.1021/jo9902143
• 作为产物：
  描述：

  (2R)-3-(tert-butyldimethylsilyloxy)-2-methylpropanal 、 Tributyl-[1-(4-methoxy-benzyloxymethyl)-buta-1,2-dienyl]-stannane 在 三氟化硼乙醚 作用下， 以75%的产率得到(2R,3R,4S)-1-(tert-Butyl-dimethyl-silanyloxy)-7-(4-methoxy-benzyloxy)-2,4-dimethyl-hept-5-yn-3-ol
  参考文献：
  名称：

  Synthesis of a syn,syn,syn,syn-Stereopentad Precursor of the Marine Sponge Polyketide Callystatin A

  摘要：

  A C13-22 syn,syn,syn,syn-stereopentad precursor of the cytotoxic polyketide callystatin A has been prepared. The synthesis involved BF3-promoted addition of the (M)-allenylstannane 28 to the alpha-methyl-beta-OTBS aldehyde 8 to afford the syn,syn adduct homopropargylic alcohol 29. Protection as the cyclic anisylidene acetal 31 and reduction of the acetylenic triple bond with Red-Al gave the (E)-allylic alcohol 32. This was subjected to Sharpless asymmetric epoxidation and subsequent treatment with an ethylcopper reagent to yield diol 34; hydrogenolysis of the derived tosylate 37 with LiBEt3H afforded 38. Acetal hydrogenolysis with DIBAl-H and oxidation yielded aldehyde 40 which was subjected to Horner-Emmons homologation to afford ester 41. This ester was converted to ester 44, an intermediate in the Kobayashi synthesis, with which it was found to be identical.

  DOI：

  10.1021/jo9902143

文献信息

• Synthesis of a <i>syn,syn,syn,syn</i>-Stereopentad Precursor of the Marine Sponge Polyketide Callystatin A
  作者：James A. Marshall、Russell N. Fitzgerald

  DOI：10.1021/jo9902143

  日期：1999.6.1

  A C13-22 syn,syn,syn,syn-stereopentad precursor of the cytotoxic polyketide callystatin A has been prepared. The synthesis involved BF3-promoted addition of the (M)-allenylstannane 28 to the alpha-methyl-beta-OTBS aldehyde 8 to afford the syn,syn adduct homopropargylic alcohol 29. Protection as the cyclic anisylidene acetal 31 and reduction of the acetylenic triple bond with Red-Al gave the (E)-allylic alcohol 32. This was subjected to Sharpless asymmetric epoxidation and subsequent treatment with an ethylcopper reagent to yield diol 34; hydrogenolysis of the derived tosylate 37 with LiBEt3H afforded 38. Acetal hydrogenolysis with DIBAl-H and oxidation yielded aldehyde 40 which was subjected to Horner-Emmons homologation to afford ester 41. This ester was converted to ester 44, an intermediate in the Kobayashi synthesis, with which it was found to be identical.